CN103396442B - Water soluble vitamin C sodium metaphosphate calcium and preparation method thereof - Google Patents
Water soluble vitamin C sodium metaphosphate calcium and preparation method thereof Download PDFInfo
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- CN103396442B CN103396442B CN201310367703.3A CN201310367703A CN103396442B CN 103396442 B CN103396442 B CN 103396442B CN 201310367703 A CN201310367703 A CN 201310367703A CN 103396442 B CN103396442 B CN 103396442B
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Abstract
The invention discloses a kind of water-soluble vitamin c sodium phosphate calcium, its structural formula is shown below:
Description
Technical field
The present invention relates to a kind of foodstuff additive or fodder additives and preparation method thereof, specifically relate to a kind of Water soluble vitamin C sodium metaphosphate calcium and preparation method thereof.
Technical background
Vitamins C is L-AA again, is the necessary nutritive ingredient of people, animal, fowl and aquatic product.Vitamins C with improve immune response, hormone sensitive lipase gene, mineral absorption, metabolism are all closely related.Therefore, vitamins C is also improve disease resistance, growth promoting effects, necessary material of preventing and curing diseases.But vitamins C is to light, thermoae sensitivity, enol form chemical structure due to L-AA brings up it and easily discharges hydrogen (H) atom, thus the impact of the factor such as light, heat is subject to Oxidative demage, particularly under high temperature illumination condition, oxidising process is, reduced form vitamins C is first oxidized to dehydroascorbate, if when being further oxidized to diketogulonic acid, just Vitamin C activity is lost, boiling also very easily destroys vitamins C, and the metal ion of lower concentration can accelerate ascorbic destruction especially in the basic conditions.
Vitamin C phosphoric ester (also known as L-AA-2-phosphoric acid ester) is the vitamin C derivatives of a kind of high stability of world market appearance in recent years, and it is obtained through esterification by L-AA and phosphoric acid agent.Because L-AA molecule 2 hydroxyls are esterified, it is made to have higher tolerance and stability to oxygen, acid, alkali in high temperature, water, air, enter in organism, under phosphoesterase action, be hydrolyzed dephosphorylate base be converted into L-AA and play a role, with vitamins C, there is identical biological activity.Therefore, be widely used at present in fields such as cultivation, feeds.
At present, common vitamin C phosphoric ester salt has vitamins C calcium phosphate, vitamins C sodium phosphate and Magnesium Ascorbyl Phosphate, their principal synthetic route for utilizing vitamins C, POCl
3, acetone, pyridine, the raw materials such as methyl alcohol, ion exchange resin exchanges.Complex process, consumption of organic solvent is large, POCl
3, pyridine toxicity is large, waste water is many and be difficult to process, and yield is low, and cost is high.
Sodium ascorbyl phosphate calcium is one of L-AA-2-phosphoric acid ester series product, and the molecular formula of the sodium ascorbyl phosphate calcium of report is C at present
6h
6o
9pCaNa, in molecule, calcium sodium mol ratio is 1:1, and the method for synthesizing this sodium ascorbyl phosphate calcium mainly utilizes calcium ascorbate at CaCl
2make catalyzer, Ca (OH)
2adjustment pH to 11 ~ 11.5 exist down and Trisodium trimetaphosphate reacts, and the six-ring of Trisodium trimetaphosphate is opened in the basic conditions, and chain-like structure breaks to form orthophosphoric acid salt vitamin C phosphoric ester simultaneously.This method needs to add excessive Trisodium trimetaphosphate and reacts completely to make calcium ascorbate, reduces free vitamin C calcium, and in reaction formula, calcium ion concn is too high, and the water-soluble decline of resultant of reaction, simultaneously due to Ca (OH)
2the rate of addition of solution is difficult to control and temperature controlled relation, the six-ring of Trisodium trimetaphosphate has part chain to rupture thoroughly not formed trimerization or two poly-phosphate or vitamin C phosphoric ester after opening, the calcium ion concn of the sodium ascorbyl phosphate calcium of this kind of method synthesis is higher, water-soluble bad, there is partial flocculation (polyphosphoric acid salt, phosphoric acid ester) calcium phosphate precipitation, the bioavailability of polyphosphate is not high simultaneously, is difficult to enzymolysis and is absorbed by animal.In order to ensure the transformation efficiency of calcium ascorbate, increasing the charging capacity of Trisodium trimetaphosphate in reactant, impelling phosphatic content to improve, by product increases.In corresponding sodium ascorbyl phosphate calcium, the content (in vitamins C) of effective stable vitamin C is only between 35% ~ 39%, and the quality of sodium ascorbyl phosphate calcium can not effectively improve, and what constrain product utilizes field.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Water soluble vitamin C sodium metaphosphate calcium and preparation method thereof, and the calcium sodium mol ratio of Water soluble vitamin C sodium metaphosphate calcium of the present invention is 1:4, good water solubility; And effective stable vitamin C content (in vitamins C) >=42%; Preparation method of the present invention is for raw material with calcium ascorbate and Trisodium trimetaphosphate, pH is regulated with NaOH, in reaction process, solution is in clear, proportion speed, does not need excess reactant, so product purity is high, by product is few, Trisodium trimetaphosphate ring-type is opened and is thoroughly become orthophosphoric acid salt, good water solubility, without flocculence material and calcium precipitation.
For solving the problems of the technologies described above, the invention provides a kind of Water soluble vitamin C sodium metaphosphate calcium, its structural formula is as follows:
In formula, the mol ratio of calcium sodium is 1:4, and in molecule, calcium ion concn is lower, better water-soluble, effectively stable vitamins C (in vitamins C) >=42%, effective constituent >=42% after 3h at 160 DEG C of temperature, good stability.
Present invention also offers the preparation method of this Water soluble vitamin C sodium metaphosphate calcium, be with calcium ascorbate and Trisodium trimetaphosphate for raw material, add catalyzer, and obtain by NaOH adjust ph.
Be specially: by molfraction, by soluble in water for 1 part of calcium ascorbate, add 0.5 ~ 0.8 part of Trisodium trimetaphosphate, be 11 ~ 11.5 by NaOH solution adjust ph, in the presence of a catalyst, react 20 ~ 30h under room temperature, be then drying to obtain sodium ascorbyl phosphate calcium.
Described catalyzer is NaH
2pO
4, Ca (H
2pO
4)
2or NaCl.
Described NaOH solution to be massfraction be 30% the NaOH aqueous solution.
Described drying is spraying dry, and inlet temperature is 160 ~ 200 DEG C, and air outlet temperature is 85 ~ 105 DEG C, or vacuum-drying, and vacuum tightness is 15 ~ 20Pa, and temperature is 40 ~ 70 DEG C.
With existing preparation sodium ascorbyl phosphate calcium (C
6h
6o
9pCaNa) method is compared, and the present invention's sodium hydroxide adjust ph, adds the solvability of reaction product, product can be kept to be reacted to and finally carry out all in the liquid phase, produces without precipitation and gelling phenomenon.Eliminate CaCl
2catalyzer, CaCl
2make catalyzer, calcium concentration own strengthens, if use NaOH adjust ph, CaCl simultaneously
2just do not have the effect of catalyzer, the two reaction generates Ca (OH)
2precipitation, reaction solution also can be made to become muddy, and by product increases; Reduce the consumption of Trisodium trimetaphosphate, make the mol ratio of calcium ascorbate and Trisodium trimetaphosphate be 1:1, reduce by product and generate, target product sodium ascorbyl phosphate calcium ((C
6h
6o
9p)
2caNa
4) content be greater than 95%, reach food grade requirement.
Chemical equation:
Water-soluble vitamin c sodium phosphate calcium ((C of the present invention
6h
6o
9p)
2caNa
4) with the sodium ascorbyl phosphate calcium (C of prior art
6h
6o
9pCaNa) compare, as can be seen from molecular formula, the calcium sodium mol ratio of prior art is 1:1, and the calcium sodium mol ratio of product of the present invention is then 1:4, and more than the calcium ion concn drop by half in molecule, the water-soluble of product significantly improves, and solution is without precipitation.Reaction of the present invention from start to finish solution is transparent, can extend the reaction times, and the consumption of Trisodium trimetaphosphate reduces, and quality product also increases, and effectively stable Vitamin C content reaches between 42% ~ 45%.Due to the good water solubility of product of the present invention, after purification, use methanol extraction crystallization, can reach the standard of foodstuff additive completely, it is low that it has cost, technique is simple, be widely used, the advantage of good stability, can be applied in the product of cake, biscuit, candy, bread etc., also improve the quality of life of people simultaneously, there is very high social value.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
200mL deionized water is joined in the four-necked bottle of 500mL band stirring, add 0.3mol calcium ascorbate (C
12h
14o
12ca), open and stir, add 0.15mol Trisodium trimetaphosphate, the NaOH solution with 30% regulates PH to 11 ~ 11.5, and temperature controls below 25 DEG C, insulation 24h.Spraying dry, inlet temperature 160 DEG C ~ 200 DEG C, air outlet temperature 85 DEG C ~ 105 DEG C.
Basic mechanical design feature index:
1, effective stable vitamin C content (in vitamins C):
Current content detection method measures with ultraviolet spectrophotometer, and product is dissolved dilution in damping fluid, at 262nm wavelength place side maximum absorbance, calculates content, after testing, calculates, water-soluble vitamin c sodium phosphate calcium ((C
6h
6o
9p)
2caNa
4) in effective stable vitamin C content (in vitamins C)>=42%
2, water-soluble:
Under normal temperature, in 90g water, add 10g water-soluble vitamin c sodium phosphate calcium ((C
6h
6o
9p)
2caNa4), be made into the aqueous solution of 10%, ultrasonic oscillation dissolves 1 minute, the transparent state of solution, without significantly precipitation and flocculation.
3, stability:
5g water-soluble vitamin c sodium phosphate calcium ((C is placed in weighing bottle in forced air oven
6h
6o
9p)
2caNa
4), timing when being heated to 160 DEG C, respectively at the content detecting effective vitamin C in water-soluble vitamin c sodium phosphate calcium after 1h, 2h, 3h, the results are shown in Table 1, result show product of the present invention at 160 DEG C, heat 3h after effective vitamin C content still higher than 42%.Illustrate that the effective vitamin C loss in product of the present invention is little, this product has stronger stability, substantially meets the interpolation requirement of variant production (food, makeup and feed).
Table 1: water-soluble vitamin c sodium phosphate calcium ((C
6h
6o
9p)
2caNa
4) stability test result synopsis
This product can be used for fodder additives.
Embodiment 2:
200mL deionized water is joined in the four-necked bottle of 500mL band stirring, add 0.3mol calcium ascorbate, open and stir, add 0.24mol Trisodium trimetaphosphate, the NaOH solution with 30% regulates pH to 11 ~ 11.5, and temperature controls below 25 DEG C, insulation 24h.Separate out rear filtration completely with isopyknic ethanol mix and blend sodium ascorbyl phosphate calcium, use washing with alcohol.Vacuum-drying, vacuum tightness 15 ~ 20Pa, temperature 3 ~ 7 DEG C, dry 6 hours, repeatedly can purify and reach specification of quality.
This product is used for food or cosmetic industry.
Embodiment 3:
200mL deionized water is joined in the four-necked bottle of 500mL band stirring, add 0.3mol calcium ascorbate, open and stir, add 0.18mol Trisodium trimetaphosphate, the NaOH solution with 30% regulates pH to 11 ~ 11.5, adds 8.3mmol SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4), temperature controls below 25 DEG C, insulation 24h.Spraying dry, inlet temperature 160 DEG C ~ 200 DEG C, air outlet temperature 85 DEG C ~ 105 DEG C.
This product is used for feedstuff industry.
Embodiment 4:
200mL deionized water is joined in the four-necked bottle of 500mL band stirring, add 0.3mol calcium ascorbate, open and stir, add 0.21mol Trisodium trimetaphosphate, NaOH solution with 30% regulates pH to 11 ~ 11.5, add 17.1mmol sodium-chlor (NaCl), temperature controls below 25 DEG C, insulation 24h.Spraying dry, inlet temperature 160 DEG C ~ 200 DEG C, air outlet temperature 85 DEG C ~ 105 DEG C.
This product is used for feedstuff industry.
Embodiment 5:
200mL deionized water is joined in the four-necked bottle of 500mL band stirring, add 0.3mol calcium ascorbate, open and stir, add 0.195mol Trisodium trimetaphosphate, the NaOH solution with 30% regulates pH to 11 ~ 11.5, adds 4mmol monocalcium phosphate (Ca (H
2pO
4)
2), temperature controls below 25 DEG C, insulation 24h.Spraying dry, inlet temperature 160 DEG C ~ 200 DEG C, air outlet temperature 85 DEG C ~ 105 DEG C.
This product is used for feedstuff industry.
Embodiment 6:
300mL deionized water is joined in the four-necked bottle of 1000mL band stirring, add 0.3mol calcium ascorbate, open and stir, add 0.20mol Trisodium trimetaphosphate, the NaOH solution with 30% regulates pH to 11 ~ 11.5, and temperature controls below 25 DEG C, insulation 24h.With isopyknic ethanol mix and blend sodium ascorbyl phosphate calcium, filter after separating out completely, with washing with alcohol, vacuum-drying, vacuum tightness 15 ~ 20Pa, temperature 3 ~ 7 DEG C of dry 6h.
This product is used for food or cosmetic industry.
Claims (1)
1. the preparation method of water-soluble vitamin c sodium phosphate calcium, it is characterized in that: by molfraction, by soluble in water for 1 part of calcium ascorbate, add 0.5 ~ 0.8 part of Trisodium trimetaphosphate, be 11 ~ 11.5 by NaOH solution adjust ph, in the presence of a catalyst, react 20 ~ 30h under room temperature, be then drying to obtain sodium ascorbyl phosphate calcium;
The structural formula of described water-soluble vitamin c sodium phosphate calcium is:
Described catalyzer is NaH
2pO
4, Ca (H
2pO
4)
2or NaCl;
Described NaOH solution to be massfraction be 30% the NaOH aqueous solution;
Described drying is spraying dry, and inlet temperature is 160 ~ 200 DEG C, and air outlet temperature is 85 ~ 105 DEG C;
Or described drying is vacuum-drying, vacuum tightness 15 ~ 20Pa, temperature is 40 ~ 70 DEG C.
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|---|---|---|---|---|
| CN104304680A (en) * | 2014-10-28 | 2015-01-28 | 安徽天寅生物科技有限公司 | L-ascorbic acid-2-phosphate compound and preparation method and application thereof |
Citations (6)
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|---|---|---|---|---|
| US4647672A (en) * | 1985-06-25 | 1987-03-03 | Kansas State University Research Foundation | Ascorbate 2-polyphosphate esters and method of making same |
| US5110950A (en) * | 1991-06-12 | 1992-05-05 | Kansas State University Research Foundation | Method of preparing 2-phosphorylated compounds of ascorbic acid |
| CN1193626A (en) * | 1997-03-18 | 1998-09-23 | 弗·哈夫曼-拉罗切有限公司 | Manufacture of ascorbyl monophosphates |
| CN1357549A (en) * | 2000-12-08 | 2002-07-10 | 北京桑普生物化学技术有限公司 | Practical prep. of L-ascorbic acid 2-monophosphate |
| CN1491952A (en) * | 2003-09-27 | 2004-04-28 | 江苏江山制药有限公司 | Preparation of VC-2 phosphate ester salt |
| CN1760199A (en) * | 2004-10-13 | 2006-04-19 | 华北制药集团有限责任公司 | Method for preparing L-ascorbic acid-2-phosphate ester and salt |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585853B (en) * | 2009-06-30 | 2011-07-13 | 安徽泰格生物技术股份有限公司 | Preparation or vitamin C calcium phosphate |
| CN102276651A (en) * | 2011-06-28 | 2011-12-14 | 无锡市跨克微营养素有限公司 | Preparation method of L-ascorbic acid-2-sodium phosphate |
| CN102702264B (en) * | 2012-05-28 | 2015-07-15 | 石药集团维生药业（石家庄）有限公司 | Method for preparing feed grade L-ascorbate-2-phosphate |
-
2013
- 2013-08-21 CN CN201310367703.3A patent/CN103396442B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647672A (en) * | 1985-06-25 | 1987-03-03 | Kansas State University Research Foundation | Ascorbate 2-polyphosphate esters and method of making same |
| US5110950A (en) * | 1991-06-12 | 1992-05-05 | Kansas State University Research Foundation | Method of preparing 2-phosphorylated compounds of ascorbic acid |
| CN1193626A (en) * | 1997-03-18 | 1998-09-23 | 弗·哈夫曼-拉罗切有限公司 | Manufacture of ascorbyl monophosphates |
| CN1357549A (en) * | 2000-12-08 | 2002-07-10 | 北京桑普生物化学技术有限公司 | Practical prep. of L-ascorbic acid 2-monophosphate |
| CN1491952A (en) * | 2003-09-27 | 2004-04-28 | 江苏江山制药有限公司 | Preparation of VC-2 phosphate ester salt |
| CN1760199A (en) * | 2004-10-13 | 2006-04-19 | 华北制药集团有限责任公司 | Method for preparing L-ascorbic acid-2-phosphate ester and salt |
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